Investigation of ideal zirconium-doped perovskite-type ceramic membrane materials for oxygen separation

Zirconium-doped perovskite-type membrane materials of BaCo0.4Fe0.6-xZrxO3-delta (x = 0-0.4) with mixed oxygen ion and electron conductivity were synthesized through a method of combining citric and EDTA acid complexes. The results of X-ray diffraction (XRD), oxygen temperature-programmed desorption (O-2-TPD) and hydrogen temperature-programmed reduction (H-2-TPR) showed that the incorporation of proper amount of zirconium into BaCo0.4Fe0.6O3-delta could stabilize the ideal and cubic structure of perovskite. Studies on the oxygen permeability of the as-synthesized membrane disks under air/He gradient indicated that the content of zirconium in these materials had great effects on oxygen permeation flux, activation energy for oxygen permeation and operation stability. The high oxygen permeation flux of 0.90 ml cm(-2) min(-1) at 950degreesC, the single activation energy for oxygen permeation in the range of 600-950 degreesC and the long-term operation stability at a relatively lower operational temperature of 800 degreesC under air/He gradient were achieved for the BaCo0.4Fe0.4Zr0.2O3-delta material. Meanwhile, the effect of carbon dioxide on structural stability and oxygen permeability of this material was also studied in detail, which revealed that the reversible stability could be attained for it. (C) 2002 Elsevier Science B.V. All rights reserved.

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Titanium-based perovskite-type mixed conducting ceramic membranes for oxygen permeation

A titanium-based perovskite-type oxide was synthesized by an improved method of combining EDTA acid and citric acid complexes. High structural stability, good sintering ability, and relatively high oxygen permeation flux were obtained simultaneously for disks synthesized from this ceramic oxide. (C) 2002 Elsevier Science B.V All rights reserved.

Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.

In situ high temperature X-ray diffraction studies of mixed ionic and electronic conducting perovskite-type membranes

Phase structure and stability of three typical mixed ionic and electronic conducting perovskite-type membranes, SrCo0.8Fe0.2O3-delta (SCF), Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) and BaCo0.4Fe0.4Zr0.2O3-delta (BCFZ) were studied by in situ high temperature X-ray diffraction at temperatures from 303 to 1273 K and under different atmospheres (air, 2% O-2 in Ar and pure Ar) at 1173 K. By analyzing their lattice parameters the thermal expansion coefficients (TECs) of BSCF, SCF and BCZF are obtained to be 11.5 x 10(-6) K-1, 17.9 x 10(-6) K-1 and 10.3 x 10(-6) K-1, respectively. A relationship between phase stability and TEC was proposed: the higher is the TEC, the lower is the operation stability of the perovskite materials. (C) 2005 Elsevier B.V. All rights reserved.

Patterning and photolumine scent properties of perovskite-type organic/inorganic hybrid luminescent films by soft lithography

Perovskite-type organic/inorganic hybrid layered compound (C6H5C2H4NH3)(2)PbI4 was synthesized. The patterning Of (C6H5C2H4NH3)(2)PbI4 thin films on silicon substrate was realized by the micromolding in capillaries (MIMIC) process, a kind of soft lithography. Bright green luminescent stripes with different widths (50, 15, 0.8 mum) have been obtained. The structure and optical properties Of (C6H5C2H4NH3)(2)PbI4 films were characterized by X-ray diffraction (XRD), UV/Vis absorption and photoluminescence excitation and emission spectra, respectively. It is shown that the organic-inorganic layered (C6H5C2H4NH3)(2)PbI4 film was c-axis oriented, paralleling to the substrate plane. Green exciton emission at 525 nm was observed in the film, and the explanations for it were given.

Preparation, characterization and luminescent properties of MCM-41 type materials impregnated with rare earth complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.

Evaluation of bond covalency and bond valence in Sr-doped perovskite-type compounds

Formulas for decomposing of complex crystals to a sum of binary crystals are described and applied to the study of bond covalency in La1-xSrxFeO3 (0.0 less than or equal to x less than or equal to 0.9) and Ca1-xSrxMnO3 (0.0 less than or equal to x less than or equal to 0.5). The bond valence is treated by bond-valence sums scheme. The results indicate that, for both compounds, with the increasing doping level, the bond covalency and bond valence show the same trend, namely, larger bond covalency corresponds to higher bond valence. For La1-xSrxFeO3, with the increase of doping level, the bond covalency of La-O, Ca-O decreases in the orthorhombic (0.0 less than or equal to x less than or equal to 0.2) and rhombohedral (0.4 less than or equal to x less than or equal to 0.7) systems, then increases slightly for the cubic (0.8 less than or equal to x less than or equal to 0.9) system, but that of Fe-O increases for all crystal systems. A sharp decrease in bond covalency was observed where the crystal changes from orthorhombic to rhombohedral, while a smooth trend was seen for the rhombohedral-to-cubic transition. On the other hand, for orthorhombic Ca1-xSrxMnO3, the bond covalency of Ca-O, Sr-O, and Mn-O (4-coordinate site) decreases with the increasing doping level, that of Mn-O (2-coordinate site) increases.

STUDIES ON THE PEROVSKITE-TYPE MIXED CATALYSTS OF TITANIUM SYSTEM FOR OXIDATIVE COUPLING OF METHANE - THE INFLUENCE OF CALCINATION TEMPERATURE

The correlations of the calcination temperature, structure and catalytic activity for the oxidative coupling of methane on the LiLa0.5Ti0.5O2+lambda catalysts whose main phase and major active phase is Perovskite-type ternary complex oxide LaTi1-yLiyO3-lambda have been studied. The surface and bulk structures of the catalysts were characterized by means of XRD, XPS, IR, BET and so on, The results cleary indicated that the effect of calcination temperature on the activity for the oxidative coupling of methane is twofold. On one hand, it is favorable for Li+ substitution for Ti3+ to enter into the lattice of LaTiO3 and produce more oxygen vacancies in which active oxygens are formed; however, excessively high calcination temperature make the amount of Li+ substitution for Ti3+ lower, due to a little change of structure or phases for the catalyst. On the other hand, the conversion of CH4 drops because of the decrease of surface area, when the calcination temperature is raised.

A STUDY OF THE CATALYTIC PROPERTIES OF PEROVSKITE-TYPE OXIDES LAMNYCO1-YO3 .2. THE INTERACTION BETWEEN TRANSITION-METAL IONS AND THEIR CATALYTIC PROPERTY IN AMMONIA OXIDATION

It has been found that the interaction between the two transition metal Mn, Co ions on B-site and their Redox property an the important factors influencing the NO-selectivity in ammonia oxidation. The NO-selectivity is related to the redox ability of Mn3+

PREPARATION, CRYSTAL-STRUCTURE, AND VIBRATIONAL-SPECTRA OF PEROVSKITE-TYPE MIXED OXIDES LAM(Y)M'(1-Y)O(3) (M,M'=MN, FE, CO)

Three series of samples LaMnyCo1-yO3+/-lambda, LaFeyMn1-yO3+/-lambda, and LaFeyCo1-yO3+/-lambda (y = 0.0 to 1.0) with Perovskite structure were prepared by an explosion method different from the generally used ceramic techniques. The variation of crystal

A STUDY OF CATALYTIC PROPERTIES OF PEROVSKITE-TYPE OXIDES LAMNYCO1-YO3 .1. THE RELATIONSHIP BETWEEN THE TYPE OF OXYGEN SPECIES AND THE CATALYTIC PROPERTY IN AMMONIA OXIDATION

The type of oxygen species in perovskite-type oxides LaMnyCo1-yO3 (y = 0.0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0) has been studied by means of XRD, XPS and TPD. The catalytic activity in ammonia oxidation was also investigated. It was found that there were three desorption peaks in TPD curve corresponding to three types of oxygen species (alpha, beta, beta'). The desorption temperatures were 293 K less-than-or-equal-to T(alpha) less-than-or-equal-to 773 K, 773 K less-than-or-equal-to T(beta) less-than-or-equal-to K and T(beta') greater-than-or-equal-to 1073 K respectively. The relationship among the composition, structure and the catalytic property of.the catalyst was correlated and could be explainned with a model based on solid defect reaction and the interaction between Co and Mn ions. The adsorption strength and quantity of a oxygen are proportional to the catalytic activity. The, result indicates that the synergetic effect between B-site ions seems to the benefit of the ammonis oxidation reaction.